ab initio calculation study on vibrational spectra of C_2B_(10)H_(12),NB_(11)H_(12) and C_2B_(10)H_(11)Cl

Geometrical optimization and theoretical calculation of the vibrational frequencies have been performed for C2B10H12, NB11H12 and C2B10Cl by using Gaussian 92 program at 6-31G basis set. The results obtained in this work are in agreement with experimental ones. The optimized geometry and vibrational spectra show that the icosahedral configuration remains unchanged upon converting from B12H122- to the title compounds. The vibrational spectrum of C2B10H11Cl features the absence of C-Cl stretching vibration. But the (C2B10H11)-Cl vibration mode in the low frequency region is as the case for two-atom molecules if the group (C2B10H11) is considered as a pseudoatom     

The quantum mechanical calculation of rotational spectra. A comparison of methods for C2H2, HCN, HNC, HCO+, N2H+, CO and N2. Predictions for HCNH+, COH+, HBO, HBNH, and HBF+

Rotational frequencies determined with ab initio molecular orbital theory can play an important role in guiding spectroscopic searches for new molecules and in corroborating the assignment of unidentified lines, from the laboratory and from space. In a systematic study of 22 levels of molecular orbital theory, CISD/6-311G** gave rotational frequencies to an accuracy of +/- 0.4 GHz when an empirical correction is applied to the results for C2H2,HCN, HNC, HCO+, N2H+, CO, and N2. Larger errors can be expected when there are large vibrational effects on the rotational constants, as exemplified by COH+. Predicted J = 0--> 1 rotational frequencies using these methods are 73.9 +/- 0.4 GHz for HCNH+, 78.6 +/- 0.4 GHz for HBO, 65.8 +/- 0.4 GHz for HBNH, and 72.1 +/- 0.4 GHz for HBF+.     

Vibrational spectra and structure of CH3Cl:(H2O)2 and CH3Cl:(D2O)2 complexes. IR matrix isolation and ab initio calculations

The infrared spectra of CH3Cl + H2O isolated in solid neon at low temperature have been investigated. High concentration studies of water (0.01%-4%) and subsequent annealing lead to the formation of the ternary CH3Cl:(H2O)2 complex. Detailed vibrational assignments were made on the observed spectra of water and deuterated water engaged in the complex. In parallel, structural, energetic, and vibrational properties of the complex have been studied at the second-order M?ller-Plesset perturbation theory using several basis sets. Anaharmonic correction to the vibrational frequencies has been done with the standard second-order perturbation approach. It was shown that the ground state of the complex has a cyclic form for which the nonadditive three-body contribution was found to be around 10% of the interaction energy.     

Simple preparations of Pd6Cl12, Pt6Cl12, and Qn[Pt2Cl8+n], n=1, 2 (Q=TBA+, PPN+) and structural characterization of [TBA][Pt2Cl9] and [PPN]2[Pt2Cl10].C7H8

The hexanuclear Pd6Cl12, i.e., the crystal phase classified as beta-PdCl2, was obtained by reacting [TBA]2[Pd2Cl6] with AlCl3 (or FeCl3) in CH2Cl2. The action of AlCl3 on PtCl42-, followed by digestion of the resulting solid in 1,2-C2H4Cl2 (DCE), CHCl3, or benzene, produced Pt6Cl12.DCE, Pt6Cl12.CHCl3, or Pt6Cl12.C6H6, respectively. Treating [TBA]2[PtCl6] with a slight excess of AlCl3 afforded [TBA][Pt2Cl9], whose anion was established crystallographically to be constituted by two "PtCl6" octahedra sharing a face. Dehydration of H2PtCl6.nH2O with SOCl2 gave an amorphous compound closely analyzing as PtCl4, reactive with [Q]Cl in SOCl2 to yield [Q][Pt2Cl9] or [Q]2[Pt2Cl10], depending on the [Q]Cl/Pt molar ratio (Q=TBA+, PPN+). A single-crystal X-ray diffraction study has shown [PPN]2[Pt2Cl10].C7H8 to contain dinuclear anions formed by two edge-sharing PtCl6 octahedra.     

Molecular orbital predictions of the vibrational frequencies of some molecular ions

Recent spectroscopic advances have led to the first determinations of infrared vibration-rotation bands of polyatomic molecular ions. These initial detections were guided by ab initio predictions of the vibrational frequencies. The calculations reported here predict the vibrational frequencies of additional ions which are candidates for laboratory analysis. Vibrational frequencies of neutral molecules computed at three levels of theory, HF/3-21G, HF/6-31G*, and MP2/6-31G*, were compared with experiment and the effect of scaling was investigated to determine how accurately vibrational frequencies could be predicted. For 92% of the frequencies examined, uniformly scaled HF/6-31G* vibrational frequencies were within 100 cm-1 of experiment with a mean absolute error of 49 cm-1. This relatively simple theory thus seems suitable for predicting vibrational frequencies to guide laboratory spectroscopic searches for ions in the infrared. Hence, the frequencies of 30 molecular ions, many with astrochemical significance,were computed. They are CH2+, CH3+, CH5+, NH2+, NH4+, H3O+, H2F+, SiH2+, PH4+, H3S+, H2Cl+, C2H+, classical C2H3+, nonclassical C2H3+, nonclassical C2H5+, HCNH+, H2CNH2+, H3CNH3+, HCO+, HOC+, H2CO+, H2COH+, H3COH2+, H3CFH+, HN2+, HO2+, C3H+, HOCO+, HCS+, and HSiO+.     

An ab-initio study of the C3H6-HX, C2H4-HX and C2H2-HX hydrogen-bonded complexes with X=F or Cl.

MP2/6-31G** ab-initio molecular orbital calculations have been performed to obtain geometries, H-bond energies and vibrational properties of the C3H6-HX, C2H4-HX and C2H2-HX H-bonded complexes with X=F or Cl. The more pronounced effects on the structural parameters of the isolated molecules due to complexation are verified to the CC and HX bond lengths, which are directly involved in the H-bond formation. They are increased after complexation. The calculated H-bond lengths for the hydrogen complexes for X=F are shorter than those for x-Cl by about 0.55 A, whereas the corresponding experimental value is 0.58 A. The H-bond energies are essentially determined by the nature of the proton donor molecule. For X=F, the AE mean value is 20 kJ/mol, whereas it is approximately 14.5 kJ/mol for X-Cl. The H-bond energies including zero-point corrections show a good correlation with the H-bond lengths. The more pronounced effect on the normal modes of the isolated molecules after complexation occurs to the H-X stretching mode. The H-X stretching frequency is shifted downward, whereas its IR intensity is much enhanced upon H-bond formation. The new vibrational modes arising from complexation show several interesting features.     

A concerted three-body formation X+Y+C2H4 in the photodissociation of CH2XCH2Y (X,Y=Br,Cl) at 193 nm

The photodissociation of CH2XCH2Y (X,Y=Br,Cl) through absorption of 193 nm photons was investigated using product translational spectroscopy. No stable CH2BrCH2 or CH2ClCH2 was detected. The recorded time-of-flight spectra indicate that these internally excited radicals dissociated into Y+C2H4 in a concerted reaction with the first C-X bond rupture. Product anisotropy implies that the overall reaction time for three-body formation is in a fraction of rotational period. According to an asynchronous concerted reaction model, the measured spectra were simulated with product translational energy distributions coupled by asymmetric angular distributions. For the mixed halide, CH2BrCH2Cl, triple products Br+Cl+C2H4 can be originated from the cleavage of either the C-Br bond or the C-Cl bond. The results are discussed and where appropriate, comparisons with previous investigations of the related molecules are included.     

Electronic absorption spectra of C3Cl, C4Cl, and their ions in neon matrices

Electronic absorption spectra of C3Cl, C3Cl+, C3Cl-, C4Cl, and C4Cl+ have been recorded in 6 K neon matrices following mass selection. Ab initio calculations were performed (CCSD(T) and CASSCF) to identify the ground and accessible excited states of each molecule. The estimated excitation energies and transition moments aid the assignment. The absorptions observed for C3Cl are the 5(2)A' <-- X(2)A' and 3(2)A' <-- X(2)A' transitions of the bent isomer and the (2)A1 <-- X(2)B2 transition of the cyclic form in the UV (336.1 nm), visible (428.7 nm), and near-IR (1047 nm) regions, respectively. The band systems for bent C3Cl- (435.2 nm) and linear C3Cl+ (413.2 nm) are both in the visible region and correspond to 2(1)A' <-- X(1)A' and (1)pi <-- X(1)sigma+ type transitions. The C4Cl and C4Cl+ chains are linear, and the band origins of the 2(2)pi <-- X(2)pi and 2(3)pi <-- X(3)pi electronic transitions are at 427.0 and 405.7 nm. The spectral assignments are supported by analysis of the vibrational structure associated with each electronic transition.     

Observation of the pi...H hydrogen-bonded ternary complex, (C(2)H(4))(2)H(2)O, using matrix isolation infrared spectroscopy

FTIR absorption spectra of water-containing ethene:Ar matrices, with compositions of ethene up to 1:10 ethene:Ar, have been recorded. Systematically increasing the concentration of ethene reveals features in the spectra consistent with the known 1:1 ethene:water complex, which subsequently disappear on further increase in ethene concentration. At high concentrations of ethene, new features are observed at 3669 and 3585 cm(-1), which are red-shifted with respect to matrix-isolated nu(3) and nu(1) O-H stretching modes of water and the 1:1 ethene:water complex. These shifts are consistent with a pi...H interaction of a 2:1 ethene:water complex of the form (C(2)H(4)...H-O-H...C(2)H(4)). The analogous (C(2)D(4))(2)H(2)O complex shows little shifting from positions associated with (C(2)H(4))(2)H(2)O, while the (C(2)H(4))(2)D(2)O isotopomer shows large shifts to 2722.3 and 2617.2 cm(-1), having identical nu(3)(H(2)O)/nu(3)(D(2)O) and nu(1)(H(2)O)/nu(1)(D(2)O) values when compared with monomeric water isotopomers. Features at 3626.1 and 2666.2 cm(-1) are also observed and are attributed to (C(2)H(4))(2)HDO. DFT calculations at the B3LYP/6-311+G(d,p) level for each isotopomer are presented, and the predicted vibrational frequencies are directly compared with experimental values. The interaction energy for the formation of the 2:1 ethene:water complex from the 1:1 ethene:water complex is also presented.     

Reaction mechanisms of C2Cl3 + NO2 via nitro and nitrite adducts

The atmospherically and environmentally important reaction of chlorinated vinyl radical with nitrogen dioxide (C 2Cl 3 + NO 2) is investigated by step-scan time-resolved Fourier transform infrared emission spectroscopy and electronic structure calculations. Vibrationally excited products of CO, NO, Cl 2CO, and NO 2 are observed in the IR emission spectra. Geometries of the major intermediates and transition states along the potential energy surface are optimized at the B3LYP/6-311G(d) level, and their energies are refined at the CCSD(T)/6-311+G(d) level. The reaction mechanisms are characterized to be barrierless addition-elimination via nitro (C 2Cl 3-NO 2) and nitrite (C 2Cl 3-ONO) adducts. Four energetically accessible reaction routes are revealed, i.e., the decomposition of the nitrite adduct forming C 2Cl 3O + NO and its sequential dissociation to CO + NO + CCl 3, the elimination of ClNO from the nitrite adduct leading to ClNO + Cl 2CCO, the Cl-atom shift of the nitrite adduct followed by the decomposition to CCl 3CO + NO, and the O-atom shift of the nitro adduct followed by C-C bond cleavage forming ClCNO + Cl 2CO. In competition with these reactive fluxes, the back-decomposition of nitro or nitrite adducts leads to the prompt formation of vibrationally excited NO 2 and the long-lived reaction adducts facilitate the vibrational energy transfer. Moreover, the product channels and mechanisms of the C 2Cl 3 + NO 2 reaction are compared with the C 2H 3 + NO 2 reaction to explore the effect of chlorine substitution. It is found that the two reactions mainly differ in the initial addition preferentially by the N-attack forming nitro adducts (only N-attack is plausible for the C 2H 3 + NO 2 reaction) or the O-attack forming nitrite adducts (O-attack is slightly more favorable and N-attack is also plausible for the C 2Cl 3 + NO 2 reaction). The addition selectivity can be fundamentally correlated to the variation of the charge density of the end carbon atom of the double bond induced by chlorine substitution due to the electron-withdrawing effect of chlorine groups.     

Infrared-vacuum ultraviolet pulsed field ionization-photoelectron study of C2H4(+) using a high-resolution infrared laser

The infrared (IR)-vacuum ultraviolet (VUV)-pulsed field ionization-photoelectron (IR-VUV-PFI-PE) spectrum for C2H4(X1A(g), v11 = 1, N'(Ka'Kc') = 3(03)) in the VUV range of 83,000-84,800 cm(-1) obtained using a single mode infrared laser revealed 24 rotationally resolved vibrational bands for the ion C2H4(+)(X2B(3u)) ground state. The frequencies and symmetry of the vibrational bands thus determined, together with the anharmonic frequency predictions calculated at the CCSD(T)/aug-cc-pVQZ level, have allowed the unambiguous assignment of these vibrational bands. These bands are mostly combination bands. The measured frequencies of these bands yield the fundamental frequencies for v8+ = 1103 +/- 10 cm(-1) and v10+ = 813 +/- 10 cm(-1) of C2H4(+)(X2B(3u)), which have not been determined previously. The present IR-VUV-PFI-PE study also provides truly rovibrationally selected and resolved state-to-state cross sections for the photoionization transitions C2H4(X1A(g); v11, N'(Ka'Kc')) --> C2H4(+)(X2B(3u); vi+, N+(Ka+Kc+)), where N'(Ka'Kc') denotes the rotational level of C2H4(X1A(g); v11), and vi+ and N+(Ka+Kc+) represent the vibrational and rotational states of the cation.     

Association reactions at low pressure. III. The C2H2+/C2H2 system

The association reactions, C4H2(+) + C2H2 and C4H3(+) + C2H2 have been examined at pressures between 8 x 10(-8) and 1 x 10(-4) Torr at 298 K in an ion cyclotron resonance mass spectrometer. Association occurred via two different mechanisms. At pressures below approximately 2 x 10(-6) Torr, the association was bimolecular having rate coefficients k2 = 2.7 x 10(-10) cm3 s-1 and 2.0 x 10(-10) cm3 s-1 for C4H2+ and C4H3+, respectively. At pressures above approximately 2 x 10(-6) Torr, termolecular association was observed with rate coefficients, k3 = 5.7 x 10(-23) cm6 s-1 and 1.3 x 10(-23) cm6 s-1 for C4H2+ and C4H3+, respectively, when M = C2H2. The termolecular rate constants with N2, Ar, Ne, and He as the third body, M, are also reported. We propose that the low pressure bimolecular association process was the result of radiative stabilization of the complex and the termolecular association process was the result of collisional stabilization. Elementary rate coefficients were obtained and the lifetime of the collision complex was > or = 57 microseconds for (C6H4+)* and > or = 18 microseconds for (C6H5+)*. At pressures below 1 x 10(-6) Torr, approximately 11% of the (C6H4+)* were stabilized by photon emission and the remaining approximately 89% reverted back to reactants, while approximately 24% of the (C6H5+)* were stabilized by photon emission and the remaining approximately 76% reverted back to reactants. The ionic products of the C2H2(+) + C2H2 reaction, C4H2+ and C4H3+, were found to be formed with enough internal energy that they did not react by the radiative association channel until relaxed by several nonreactive collisions with the bath gas.     

Lifetime of C2Cl4(-) ions produced by nondissociative electron attachment to C2Cl4

The lifetimes of long-lived C2Cl4(-) ions formed by Rydberg electron transfer in K(np)/C2Cl4 collisions are investigated using a Penning ion trap. Measurements at high n, n > or = 30, show that low-energy electron attachment to C2Cl4 leads to the production of C2Cl4(-) ions with a broad range of lifetimes that extends up to at least 1 ms. This is attributed to capture by molecules in different initial vibrational states. At low n, internal-to-translational energy transfer in postattachment interactions between the product K+ and C2Cl4(-) ions becomes important and leads to a substantial increase in ion lifetimes.     

Electron attachment to C(2)Cl(4) and Trojan horse ionization

In a recent study of tetrachloroethylene, the anion yield curves were analyzed using three published negative-ion Morse potentials. Unexpected ions at zero electron energy were explained by the "Trojan horse" mechanism. This communication also attributes formation of Cl(2)(-) at higher energies to a Trojan horse mechanism. Six new Morse potentials are calculated to account for the observed anion states. These combine all extant electron impact and attachment data. The electron affinity of the C(2)Cl(3) radical, 3.1(1) eV, and the C-Cl bond dissociation energy 4.0(1) eV are reported.     

复合物C6H5CH3…Ar分子间的外部振动频率

利用双光子共振电离光谱和飞行时间质谱技术在超声分子束中观察到C6H5CH3…Ar的振动光谱.借助同位素光谱效应、内转动能级和分子间振动能级的理论计算,合理地归属了涉及CH3转动和Ar原子振动的光谱,并由此获得复合物分子间各种模式的振动频率.     

Arylzinc alkoxides: [ArZnOCHPr(i)2]2 and Ar2Zn3(OCHPr(i)2)4 when Ar = C6H5, p-CF3C6H4, 2,4,6-Me3C6H2, and C6F5

From the reactions between diarylzinc compounds (Ar2Zn) and the alcohol (Pr(i)2CHOH) in toluene, the compounds [ArZn(OCHPr(i)2)]2 (Ar = C6H5, C6F5, p-CF3C6H4, and 2,4,6-Me3C6H2) have been isolated and shown to exist in equilibra with the trinuclear complexes Ar2Zn3(OCHPr(i)2)4 and Ar2Zn when Ar = C6H5, C6F5, and p-CF3C6H4. The trinuclear complexes have also been prepared from reactions of the Ar2Zn compounds with the alcohol, which reveals that the ease of Zn-C(aryl) bond cleavage is sensitive to the nature of the Ar group: C6H5 > 4-CF3C6H4 > C6F5. The molecular structures of Ar2Zn3(OCHPr(i)2)4 where Ar = p-CF3C6H4 and C6F5 and [ArZn(OCHPr(i)2)]2 where Ar = C6F5, p-CF3C6H4, and 2,4,6-Me3C6H2 are reported based on single-crystal X-ray diffraction studies. The X-ray structure of Zn(p-CF3C6H4)2 is also reported. The reactivity of these new compounds toward the polymerization of propylene oxide (PO) and the copolymerization of PO and CO2 have been investigated along with related reactions involving the partial hydrolysis of the Ar2Zn and R2Zn compounds, where R = t-Bu, n-Bu, and n-Oct. These results are compared with the previous studies employing Et2Zn as an organozinc precursor.     

Isomeric effects in the gas-phase reactions of dichloroethene, C2H2CL2, with a series of cations

A study of the reactions of a series of gas-phase cations (NH(4)(+), H(3)O(+), SF(3)(+), CF(3)(+), CF(+), SF(5)(+), SF(2)(+), SF(+), CF(2)(+), SF(4)(+), O(2)(+), Xe(+), N(2)O(+), CO(2)(+), Kr(+), CO(+), N(+), N(2)(+), Ar(+), F(+), and Ne(+)) with the three structural isomers of dichloroethene, i.e., 1,1-C(2)H(2)Cl(2), cis-1,2-C(2)H(2)Cl(2), and trans-1,2-C(2)H(2)Cl(2) is reported. The recombination energy (RE) of these ions spans the range of 4.7-21.6 eV. Reaction rate coefficients and product branching ratios have been measured at 298 K in a selected ion flow tube (SIFT). Collisional rate coefficients are calculated by modified average dipole orientation (MADO) theory and compared with experimental data. Thermochemistry and mass balance have been used to predict the most feasible neutral products. Threshold photoelectron-photoion coincidence spectra have also been obtained for the three isomers of C(2)H(2)Cl(2) with photon energies in the range of 10-23 eV. The fragment ion branching ratios have been compared with those of the flow tube study to determine the importance of long-range charge transfer. A strong influence of the isomeric structure of dichloroethene on the products of ion-molecule reactions has been observed for H(3)O(+), CF(3)(+), and CF(+). For 1,1-C(2)H(2)Cl(2) the reaction with H(3)O(+) proceeds at the collisional rate with the only ionic product being 1,1-C(2)H(2)Cl(2)H(+). However, the same reaction yields two more ionic products in the case of cis-1,2- and trans-1,2-C(2)H(2)Cl(2), but only proceeds with 14% and 18% efficiency, respectively. The CF(3)(+) reaction proceeds with 56-80% efficiency, the only ionic product for 1,1-C(2)H(2)Cl(2) being C(2)H(2)Cl(+) formed via Cl(-) abstraction, whereas the only ionic product for both 1,2-isomers is CHCl(2)(+) corresponding to a breaking of the C=C double bond. Less profound isomeric effects, but still resulting in different products for 1,1- and 1,2-C(2)H(2)Cl(2) isomers, have been found in the reactions of SF(+), CO(2)(+), CO(+), N(2)(+), and Ar(+). Although these five ions have REs above the ionization energy (IE) of any of the C(2)H(2)Cl(2) isomers, and hence the threshold for long-range charge transfer, the results suggest that the formation of a collision complex at short range between these ions and C(2)H(2)Cl(2) is responsible for the observed effects.     

New molecular perovskites: cubic C(4)N(2)H(12).NH(4)Cl(3).H(2)O and 2-H hexagonal C(6)N(2)H(14).NH(4)Cl(3)

The room-temperature syntheses and single-crystal structures of C(4)N(2)H(12).NH(4)Cl(3).H(2)O and C(6)N(2)H(14).NH(4)Cl(3) are reported. These novel molecular perovskites contain vertex-sharing octahedral (NH(4))Cl(6) arrays which replicate the octahedral packing in the cubic (SrTiO(3)) and 2-H hexagonal (BaNiO(3)) perovskite structures, respectively. The structures are completed by doubly protonated organic cations and, for the cubic phase, water molecules. Crystal data: C(4)N(2)H(12).NH(4)Cl(3).H(2)O, M(r) = 230.56, orthorhombic, Pbcm (No. 57), a = 6.5279(13) A, b = 12.935(3) A, c = 12.849(3) A, V = 1085.0(4) A(3), Z = 4; C(6)N(2)H(14).NH(4)Cl(3), M(r) = 238.59, trigonal, Pthremacr;c1 (No. 165), a = 16.1616(2) A, c = 22.3496(4) A, V = 5055.5(2) A(3), Z = 18.     

Room-temperature chemisorption and thermal evolution of 1,1-dichloroethylene and monochloroethylene on Si(111)7 x 7: formation of vinylidene and vinylene adspecies

The room-temperature (RT) adsorption and thermal evolution of 1,1-dichloroethylene (1,1-C2H2Cl2 or iso-DCE) and monochloroethylene (C2H3Cl or MCE) on Si(111)7 x 7 have been studied by vibrational electron energy loss spectroscopy and thermal desorption spectrometry (TDS). The presence of the Si-Cl stretch at 510 cm(-1) suggests that upon adsorption iso-DCE dissociates via C-Cl bond breakage on the 7x7 surface to form mono-sigma-bonded 1-chlorovinyl (ClC=CH2) and/or di-sigma-bonded vinylidene (: C=CH(2)) adspecies. Upon annealing to 450 K, the 1-chlorovinyl adspecies undergoes further dechlorination to vinylidene adspecies, which may be converted to di-sigma-bonded vinylene (HC=CH) before dehydrogenating to hydrocarbon fragments above 580 K. TDS studies reveal both molecular desorption of iso-DCE near 350 K and C2H2 fragments near 700 K, and the presence of the latter confirms the existence of the di-sigma-bonded vinylene adspecies. Like the other chlorinated ethylene homologues, iso-DCE also exhibits TDS features of an etching product SiCl2 at 800-950 K and a dehydrochlorination product HCl at 700-900 K. Unlike iso-DCE, MCE is found to adsorb on the 7 x 7 surface predominantly through a [2 + 2] cycloaddition mechanism at RT, with similar di-sigma bonding structure as ethylene. The thermal evolution of MCE however follows that of iso-DCE, with the formation of vinylene above 580 K. Despite the lack of TDS feature attributable to HCl, weaker SiCl2 TDS feature could be observed at 800-950 K. For both iso-DCE and MCE, strong recombinative desorption of H2 is observed near 780 K. The differences in the Cl content among iso-DCE, MCE, and ethylene therefore play a key role in the RT chemisorption and thermally driven chemical processes on Si(111)7 x 7.     

Syntheses and characterization of the MF6- (M = As, Sb) salts of the simple trithietanylium PhCS3+ cation and the identity of PhCS3Cl

MF6- (M = As or Sb) salts of a simple derivative of the trithietanylium PhCSSS+, 1, were synthesized for the first time by the reaction of PhCS3Cl and AgMF6 in liquid SO2. 1SbF6 was characterized by IR, FT-Raman, and NMR spectroscopy, elemental analysis, and a preliminary X-ray crystal structure. 1AsF6 was characterized by 1H NMR and FT-Raman spectroscopy. The calculated (MPW1PW91/3-21G* or 6-31G*) geometries, 1H and 13C chemical shifts (MPW1PW91/6-311G(2DF)//MPW1PW91/3-21G*), and vibrational frequencies and intensities (MPW1PW91/6-31G*) were in satisfactory agreement with the observed values. The calculated pi type molecular orbitals of HCSSS+ (MPW1PW91/6-311+G*) and 1 (MPW1PW91/3-21G*) imply that the 6pi-CSSS+ ring has some aromatic character. 1SbF6 undergoes a metathesis reaction with NBu4Cl in liquid SO2 to give PhCS3Cl, which was characterized by vibrational spectroscopy and mass spectrometry. The evidence indicates that PhCS3Cl has the ionic formulation PhCSSS+ Cl- with significant cation-anion interactions in the solid state. ArCSSS+ SbF6- (Ar = 1-naphthyl), 14SbF6, was prepared from ArCS3Cl and AgSbF6, suggesting that the synthesis of MF6- (M = As or Sb) salts of RCSSS+ is potentially general for aryl derivatives. The structure of 14SbF6 was established by 1H and 13C NMR, IR, and FT-Raman spectroscopy, and theoretical calculations gave values in agreement with the experimental data.